US3555146A - Antiperspirant composition - Google Patents
Antiperspirant composition Download PDFInfo
- Publication number
- US3555146A US3555146A US704200A US3555146DA US3555146A US 3555146 A US3555146 A US 3555146A US 704200 A US704200 A US 704200A US 3555146D A US3555146D A US 3555146DA US 3555146 A US3555146 A US 3555146A
- Authority
- US
- United States
- Prior art keywords
- aluminum
- chloride
- zinc
- solution
- hydroxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/58—Metal complex; Coordination compounds
Definitions
- Q is a zinc chloride, iodide or bromide or hydroxychloride, hydroxy iodide or hydroxy bromide or a zirconyl chloride or hydroxy chloride
- A is chloride, bromide or iodide
- R is the coordinating moiety of a polyhydroxy compound having at least two carbon atoms and at least two hydroxy groups, with n being the number of moles for Q and at least 0.05, and with the antiperspirant preparation containing conventional cosmetic adjuvants.
- the present invention relates generally to novel metalaluminum inorganic-organic complexes which have an unexpectedly high degree of metal-aluminum ionicity and significant solubility in non-aqueous media, to methods of making such complexes, and to methods of and preparations employing such complexes in the formulation of novel and effective non-aqueous compositions which are useful as antiperspirants.
- an important consideration of the present invention is to obtain a complex of aluminum and metals (as shall be defined) which maintains substantially all of the ionicity of the aluminum and the metal and thereby achieves the optimum of antiperspirancy.
- a second consideration is to develop an antiperspirant which permits the use of aerosol dispensers, a packaging form which heretofore has not been adaptable for true antiperspirants because of many problems presented by prior antiperspirant formulations.
- aerosol dispenser has been successfully adapted to the deodorant field by the packaging of certain bactericides (e.g., zinc sulfocarbolate and hexachlorophene) in an alcohol ve- Patented Jan. 12, 1971 ICC hicle and mixed with a suitable propellant, these products do not materially affect the exudation of perspiration by the body and therefore are not true antiperspirants.
- the aerosol dispenser has had extremely limited application to the antiperspirant field because of the inability of the art to achieve a solubility in excess of about 1 to 3% (as obtained, for instance, with aluminum phenolsulfonate). In contrast, it is generally accepted that no composition is effective as an antiperspirant at less than a minimum concentration of about 10 percent of the active ingredient.
- an antiperspirant composition must inhibit perspiration in a safe and non-corrosive manner and it must be compatible with those compounds employed to propel aerosol sprays.
- such a composition should contain a minimal water content (maximum tolerable is 23%) so as to eliminate the extreme corrosion induced by aqueous media in and to the metal valves and containers (glass lined containers are much too expensive), and the product contamination which results therefrom.
- such compositions must be capable of being dissolved in the associated carrier in concentrations of at least 10%.
- the present invention is predicated upon our discovery of new complexes (coordination compounds) containing a metal selected from the group consisting of zinc and zirconium, and aluminum which complexes maintain the ionicity of the metals and thereby are highly effective as antiperspirants (astringency being the key characteristic). Furthermore, our complexes are compatible with halogenated hydrocarbon propellants, and most importantly, are soluble in non-aqueous media to provide effective concentrations of 10% or greater. We have further discovered how to make these complexes in an easy and economical fashion and to formulate effective liquid antiperspirant compositions from them which compositions are highly suited for use, inter alia, in the aerosol dispensers. We have also developed certain lotions and cremes in which our complexes are highly effective.
- a prime object of the present invention is to provide new coordination compounds (complexes) of aluminum with zinc and/or zirconium, which compounds: are readily soluble in non-aqueous media; are compatible with conventional aerosol dispenser propellants, such as the halogenated hydrocarbons; exhibit effective and safe antiperspirant action; and can be prepared in such a manner as to permit the presentation of a competitive product in the marketplace, that is, are economical to produce and do not require special glass lined containers or the like.
- Another object of the present invention is to provide new complexes of zinc-aluminum and/ or zirconiumalurninum which have etfective antiperspirant properties and can be used in the presence of metal parts without fear of corrosion or contairnination while remaining substantially non-corrosive to skin and fabric clothing.
- a further object of the present invention is to provide new complexes of zinc-aluminum and/ or zirconiumaluminum which can be dissolved in effective concentrations in non-aqueous volatile solvents while maintaining effective ionicity.
- Still another object of the present invention is to provide a composition which can be dispensed in a nonaqueous carrier as a rapidly drying spray which dries on the skin to regulate and control the exudation of perspiration from the skin contiguous thereto.
- a still further object of the present invention is to provide alcohol soluble complexes of zinc-aluminum and/ or zirconium-aluminum which are useful to form a liquid antiperspirant formulation in which the ionicity of the complex is maintained.
- Another object of the present invention is to provide an antiperspirant formulation which avoids the corrosive elfect heretofore characteristic of the prior art mineral acid salts and yet obtain an antiperspirant action of comparable effect.
- Still another object of the present invention is to provide new and useful coordination compounds of zincaluminum and/or Zirconium-aluminum which are characterized by ionicity of the coordination compounds and which obtain, in non-aqueous solvents, a solubility of at least about and to provide methods of preparing such compounds.
- n is the number of moles of Q and is at least 0.05.
- the aluminum and zinc or zirconium salts and the polyhydroxy compound thus combined, form a solution which with heat forms the complex of the present invention.
- the heating will continue until substantially all excess water is expelled from the solution and a dry product is formed.
- the solution is highly useful and drying can be omitted.
- aluminum basic chloride refers to those compounds having the empirical formula: Al (OH),,Cl wherein x is a positive integer of from 2 to 5; y is a positive integer of from 1 to 4; and x and y will always total 6.
- Aluminum basic chlorides herein contemplated are:
- polyhydroxy compound as used herein, means those organic compounds containing (prior to condensation) two or more hydroxy or substituted hydroxy groups linked to adjacent or non-adjacent carbon atoms. We specifically intended to include, although not be limited to, dihydric and polyhydric alcohols and glycol ethers.
- Suitable aluminum salts for the practice of the invention include aluminum basic chloride, aluminum basic iodide and aluminum basic bromide. Particularly fine results are obtained when an aluminum basic chloride having an aluminum to chlorine mol ratio of from about 1:3 up to about 2.1 to 1, more advantageously between about 1:1 to about 2:1, is used in the practice of the invention.
- this solution may be placed at a temperature ranging from 70 C. (under vacuum) to 120 C. (in air) and this temperature is maintained until the weight loss is equivalent to or greater than all of the free (non coordinated) moisture calculated to be present.
- This provides a dry product, that is, a product having from about 0.5 to about 20.0% retained moisture which has a solubility in SDA 40 of greater than As will appear, a friable product containing about 20% moisture can be produced, and, on the basis of 10% solids, will provide an aerosol formulation containing only about 2% water.
- the moisture content will be controlled at about maximum because this will create enhanced compatibility with halo-hydro carbon propellants.
- the complex that is, the dry product
- zirconyl chloride zirconium oxychloride
- 1,3- butanediol based on the solids content of the solution
- this solution was placed under a vacuum of about 25 inches of Hg and a temperature of about 70-95 C. was established and maintained until the weight loss is substantially equivalent to (or greater than) all of the free moisture calculated as present.
- This provides a dry product having about 0.5 to about retained moisture. This product also is soluble at greater than 10% in SDA 40.
- the starting metal salts may be of any percent solution although the water content should be reasonable since the presence of excessive water merely increases the cost of drying and too little water obstructs efiicient mixing.
- a viscous liquid we define as one possessing a viscosity at C. of from 100-300 centipoises.
- the zinc or zirconyl starting materials are preferably granular although aqueous solutions can be employed when convenient.
- the polyhydroxy compound can contain some water although if desired anhydrous compound (i.e., 100%) works well.
- the stirring of the reagents and the various steps of combination and during drying comprises an effective expedient for mixing and evaporation although when time is of no particular consideration, the stirring can be omitted without any clearly discernible impairment of product quality.
- other known techniques for encouraging a more or less rapid rate of evaporation may be used if desired; the inducement of such an increased rate being, of course, a matter of convenience and time-saving and not a factor in the quality of the complex produced therefrom.
- the application of external heat to the mixture during drying is calculated to enhance the rate of evaporation and is highly desirable although not essential. Any temperature falling between room temperature and the average boiling temperature of the mixture, i.e., about 110 C., can be used although the rate of evaporation will bear a direct relationship to the temperature selected. Our sense of time efiiciency is particularly satisfied by a temperature in the range of about to about C.
- the evaporation over heat is calculated to significantly reduce the time necessary to accomplish the final drying.
- a volume reduction to about 0.8 time the original volume provides a convenient and readily discernible measure for it is at about this amount of volume reduction that the reacting solution acquires visible viscosity.
- a preferred procedure will involve the use of drying trays which may be formed of glass or of any other material which is capable of remaining inert with respect to our ingredients. Teflon linings may prove advan tageous while iron in particular, should be avoided because it does react with the reagents to cause a disagreeable product discoloration.
- the shallow trays themselves are extremely helpful because they expose a greater area of material and thereby expedite the evaporation process.
- the evaporation phase may be accomplished at temperatures as high as C. without scorching the product while temperatures on the order of about 50 C. may also be used under a vacuum although the time required to complete the evaporation of the water from the product is extended.
- the resulting complex will have the formula wherein n is the number of moles of zirconyl chloride and always at least 0.05, A is an anion selected from the group consisting of chloride, iodide and bromide, and R is the coordinating moiety of the polyhydroxy compound as previously described.
- n is the number of moles of zinc chloride and always at least 0.05 and A and R are as defined above.
- EXAMPLE r We added 45.0 g. of 50% zirconium oxychloride (0.01 mol Zr) to 76.1 g. of hot 50% aluminum chlorhydroxide (0.35 mol Al). The gel that formed was essentially dissolved with prolonged heat and agitation and reflux at 100 C. continued for 0.5 hour. To the cloudy solution added 29.6 g. of propylene glycol and continued refluxing for two hours. The solution was filtered clear and tray dried at about 95 C. and 26 inches Hg vacuum to yield a solid which was very slowly soluble in anhydrous ethanol.
- EXAMPLE II With agitation, we added 6.9 g. of zinc chloride to 109.6 g. of 50% aluminum chlorohydroxy. After solution was complete, we added 38.0 g. of propylene glycol and heated the mixture at 95-100 C. for one hour. Next, we evaporated the clear solution to near constant weight at 70 C. and about mm. Hg pressure. The solids thus obtained were readily soluble to at least 30% by weight in anhydrous ethanol.
- EXAMPLE 111 We mixed 109.6 g. of 50% aluminum chlorhydroxide and 8.88 g. of 96% zinc chloride and heated at 95 C. for one hour. Then we added 24.5 g. of propylene glycol to the mix and the clear solution was heated an additional hour at about 95 C. The product was dried to near constant weight at 80 C. and about 10 mm. Hg pressure. The solids obtained were readily soluble in anhydrous ethanol.
- EXAMPLE IV We dissolved 17.75 g. of 96% zinc chloride in 109.6 g. of 50% aluminum chlorhydroxide and heated one hour at 95 C. To this we added 19.8 g. of propylene glycol and continued heating one hour at 95 C. The solution was then dried to near constant weight in a rotary vacuum drier at about 70 C. and 10 mm. Hg pressure. The product obtained was rapidly soluble to at least 30% in anhydrous ethanol.
- EXAMPLE V We heated 109.6 g. of 50% aluminum chlorhydroxide and 8.88 g. of 96% zinc chloride at 95 C. for one hour. We then added 47.5 g. of propylene glycol and continued heating for one hour. The resulting composition was dried at 70 C. and 10 mm. Hg pressure to a constant weight to yield a very sticky semi-solid. The product was dissolved in about 200 m1. of anhydrous methanol and redried under the same conditions to yield a very friable solid, which was extremely soluble in anhydrous ethanol.
- EXAMPLE VI We dissolved 17.75 g. of 96% zinc chloride, in 109.6 g. of 50% aluminum chlorhydroxide and heated at 95 C. for one hour. To this we added 34.6 g. of 1,3-butanediol and continued heating one hour. This composition was then evaporated to constant weight at about 70 and 10 mm. Hg pressure. The product obtained was rapidly soluble to at least 30% by weight in anhydrous ethanol.
- EXAMPLE VII We dissolved 17.75 g. of 96% zinc chloride, in 109.6 g. of 50% aluminum chlorhydroxide and heated at 95 C. for one hour. We then dissolved 51.5 g. of trimethylol propane in the hot solution and continued heating one hour. This solution was then evaporated to constant weight at 70 C. and about 10 mm. Hg. pressure. The
- EXAMPLE VII-I We added 51.4 g. of a 50% aqueous zirconium oxychloride solution (0.08 mol Zr) to 69.6 g. of a hot agitated 50% solution of aluminum chlorhydroxide (0.32 mol A1). A turbid gel, which formed immediately, was slowly dissipated with heat and agitation and the cloudy solution was refluxed at l00 C. for 0.5 hour. Next, we added 34.8 g. of propylene glycol and continued reflux for 2.0 hours. The solution filtered clear and tray dried at about 95 C. and 26 inches vacuum. The product obtained was slowly soluble to at least 30% by weight in anhydrous ethanol.
- EXAMPLE XII We added 64.4 g. of 50% zirconium oxychloride (0.10 mol Zr) to a heated 50% aqueous solution of aluminum chlorhydroxide (0.40 mol Al). The resulting gel was dissipated with heat and agitation and refluxed at 100 C. for 0.5 hour. We then added 43.6 g. of propylene glycol to the hot cloudy solution and continued refluxing for two hours. This solution was then filtered clear and transferred to a round bottom distillation apparatus equipped with agitation. With heating, the solution was concentrated a viscous but flowable mass. We then added 1100 mls. of anhydrous ethanol in 100 m1. increments and continued distilling until a total of about 900 mls. of the water-alcohol azeotrope had been removed.
- Another important aspect of the present invention is the incorporation of the coordination compounds of this invention in combination with certain of the so-called aerosol propellants such, for example, as trichloromonofluoromethane (Freon 12), dichlorotetrafluoroethane (Freon 114), monochlorodifluoromethane (Freon 22), trichlorotrifluoroethane (Freon 113), octafluorocyclobutane (Freon C 318), pentafluoromonochloroethane (Freon 115 dimethyl ether, vinyl chloride, nitrous oxide, nitrogen, 1,1-difluoroethane, and 1,1,1-chlorodifluoroethane.
- aerosol propellants such, for example, as trichloromonofluoromethane (Freon 12), dichlorotetrafluoroethane (Freon 114), monochlorodifluo
- the alcohol carrier can be any of the approved denatured ethyl alcohols such, for example, as: SDA-23A; SDA-28B; SDA 39B; SDA-39C; SDA 40; SDA 40A and the like as well as isopropyl alcohol, and the diand polyhydric alcohols.
- the diand polyhydric alcohols can be used alone or in addition to a primary 501- vent since it appears to enhance the miscibility of the solvent with the propellant.
- ethanol is truly representative of the non-aqueous solvents commercially available and solubility in ethanol is reflective of like compatibility in the other non-aqueous solvents.
- Cerosynt 1000D is a brand of glycerol monostearate manufactured by Van Dyk & Company
- Emulsynt 2400 is a brand of polyoxyethylene glycol laurate/oleate manufactured by Van Dyk & Company
- Sindar G-ll is a brand of hexachlorophene manufactured by Sindar Corporation, New York, N.Y.
- Versene Regular is a brand of tetrasodium salt of ethylenediamine tetraacetic acid manufactured by the Dow Chemical Company, Midland, Mich.
- Amerchol L101 is a lanolin-derived sterol extract manufactured by American Cholesterol Porducts, Inc.
- Freon 114 is a dichloro-tetrafluoroethane, manufactured by-Du Pont Company, Wilmington, Del.
- Freon 12 is a dichlorodifluorome
- An antiperspirant composition in the form of an aerosol consisting essentially of an aerosol propellant, an
- An antiperspirant composition in accordance with claim 1 which contains a conventional cosmetic adju-vant. 15 67, 68
Abstract
NQ.AL2(OH)4-5A1-2R1-4H2O0.5-4
WHEREIN Q IS A ZINC CHLORIDE, IODIDE OR BROMIDE OR HYDROXYCHLORIDE, HYDROXY IODIDE OR HYDROXY BROMIDE OR A ZIRCONYL CHLORIDE OR HYDROXY CHLORIDE, A IS CHLORIDE, BROMIDE OR IODIDE, R IS THE COORDINATING MOIETY OF A POLYHYDROXY COMPOUND HAVING AT LEAST TWO CARBON ATOMS AND AT LEAST TWO HYDROXY GROUPS, WITH N BEING THE NUMBER OF MOLES FOR Q AND AT LEAST 0.05, AND WITH THE ANTIPERSPIRANT PREPARATION CONTAINING CONVERTIONAL COSMETIC ADJUVANTS.
Description
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US487580A US3405153A (en) | 1965-09-15 | 1965-09-15 | Metal-aluminum inorganic-organic complexes and methods of preparing same |
US70420067A | 1967-11-13 | 1967-11-13 |
Publications (1)
Publication Number | Publication Date |
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US3555146A true US3555146A (en) | 1971-01-12 |
Family
ID=27049057
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US704200A Expired - Lifetime US3555146A (en) | 1965-09-15 | 1967-11-13 | Antiperspirant composition |
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US (1) | US3555146A (en) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3981986A (en) * | 1973-11-23 | 1976-09-21 | Armour Pharmaceutical Company | Zirconium-aluminum-polyol buffered anti-perspirant complexes |
US3998788A (en) * | 1974-01-08 | 1976-12-21 | Armour Pharmaceutical Company | Aluminum-zirconium anti-perspirant systems with trace amounts of alkaline earth metals |
US4025615A (en) * | 1975-02-25 | 1977-05-24 | Armour Pharmaceutical Company | Antiperspirant complexes formed with alkali metal and ammonium zirconyl carbonates |
US4027007A (en) * | 1970-12-09 | 1977-05-31 | Colgate-Palmolive Company | Antiperspirants formulated with borax |
US4110428A (en) * | 1970-03-23 | 1978-08-29 | Lever Brothers Company | Antiperspirant composition |
US4137306A (en) * | 1973-06-05 | 1979-01-30 | Armour Pharmaceutical Company | Anhydrous antiperspirant stick compositions |
US4223010A (en) * | 1979-01-08 | 1980-09-16 | Armour Pharmaceutical Company | Basic zirconium complexes and methods of making and using in antiperspirants |
US4477579A (en) * | 1983-04-14 | 1984-10-16 | Nalco Chemical Company | Electrode coating and coated electrodes |
US4512913A (en) * | 1982-07-12 | 1985-04-23 | Owens-Corning Fiberglas Corporation | Sol-gel solution preparation |
US4545924A (en) * | 1983-06-13 | 1985-10-08 | Owens-Corning Fiberglas Corporation | Production of a magnesium chloride gel system useful in ceramics and fiber production |
US4606915A (en) * | 1981-04-23 | 1986-08-19 | Bristol-Myers Company | Antiperspirant combination containing an aluminum halohydrate and a stannic halide |
US5463098A (en) * | 1992-11-16 | 1995-10-31 | Giovanniello; Rocco | Clear antiperspirant gel stick and method for making same |
US5601809A (en) * | 1986-09-26 | 1997-02-11 | The Gillette Company | Axillary malodor neutralization |
US20010033854A1 (en) * | 2000-01-18 | 2001-10-25 | Johnson Paula Ann | Anti-microbial compositions |
US6485715B1 (en) | 2001-05-23 | 2002-11-26 | The Proctor & Gamble Company | Stable pressurized antiperspirant compositions containing dimethylether propellant and a low polarity solvent |
US20030108499A1 (en) * | 2001-07-18 | 2003-06-12 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Deodorant compositions |
US20040081632A1 (en) * | 2002-10-23 | 2004-04-29 | Parekh Jawahar C. | Novel antiperspirant/deodorant active for no white residue sticks and soft solids |
US20050191255A1 (en) * | 2000-01-18 | 2005-09-01 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Anti-microbial antiperspirant products |
-
1967
- 1967-11-13 US US704200A patent/US3555146A/en not_active Expired - Lifetime
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4110428A (en) * | 1970-03-23 | 1978-08-29 | Lever Brothers Company | Antiperspirant composition |
US4027007A (en) * | 1970-12-09 | 1977-05-31 | Colgate-Palmolive Company | Antiperspirants formulated with borax |
US4137306A (en) * | 1973-06-05 | 1979-01-30 | Armour Pharmaceutical Company | Anhydrous antiperspirant stick compositions |
US3981986A (en) * | 1973-11-23 | 1976-09-21 | Armour Pharmaceutical Company | Zirconium-aluminum-polyol buffered anti-perspirant complexes |
US3998788A (en) * | 1974-01-08 | 1976-12-21 | Armour Pharmaceutical Company | Aluminum-zirconium anti-perspirant systems with trace amounts of alkaline earth metals |
US4025615A (en) * | 1975-02-25 | 1977-05-24 | Armour Pharmaceutical Company | Antiperspirant complexes formed with alkali metal and ammonium zirconyl carbonates |
US4223010A (en) * | 1979-01-08 | 1980-09-16 | Armour Pharmaceutical Company | Basic zirconium complexes and methods of making and using in antiperspirants |
US4606915A (en) * | 1981-04-23 | 1986-08-19 | Bristol-Myers Company | Antiperspirant combination containing an aluminum halohydrate and a stannic halide |
US4512913A (en) * | 1982-07-12 | 1985-04-23 | Owens-Corning Fiberglas Corporation | Sol-gel solution preparation |
US4477579A (en) * | 1983-04-14 | 1984-10-16 | Nalco Chemical Company | Electrode coating and coated electrodes |
US4545924A (en) * | 1983-06-13 | 1985-10-08 | Owens-Corning Fiberglas Corporation | Production of a magnesium chloride gel system useful in ceramics and fiber production |
US5601809A (en) * | 1986-09-26 | 1997-02-11 | The Gillette Company | Axillary malodor neutralization |
US5463098A (en) * | 1992-11-16 | 1995-10-31 | Giovanniello; Rocco | Clear antiperspirant gel stick and method for making same |
US20010033854A1 (en) * | 2000-01-18 | 2001-10-25 | Johnson Paula Ann | Anti-microbial compositions |
US20050191255A1 (en) * | 2000-01-18 | 2005-09-01 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Anti-microbial antiperspirant products |
US6485715B1 (en) | 2001-05-23 | 2002-11-26 | The Proctor & Gamble Company | Stable pressurized antiperspirant compositions containing dimethylether propellant and a low polarity solvent |
US20030108499A1 (en) * | 2001-07-18 | 2003-06-12 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Deodorant compositions |
US20040081632A1 (en) * | 2002-10-23 | 2004-04-29 | Parekh Jawahar C. | Novel antiperspirant/deodorant active for no white residue sticks and soft solids |
US6835374B2 (en) | 2002-10-23 | 2004-12-28 | Reheis, Inc. | Antiperspirant/deodorant active for no white residue sticks and soft solids |
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Owner name: BANK AND TRUST COMPANY,MASSACHUSETTS Free format text: MORTGAGE;ASSIGNOR:REHEIS CHEMICAL COMPANY, INC.;REEL/FRAME:004586/0269 Effective date: 19860411 Owner name: BANK AND TRUST COMPANY, 225 FRANKLIN STREET, BOSTO Free format text: MORTGAGE;ASSIGNOR:REHEIS CHEMICAL COMPANY, INC.;REEL/FRAME:004586/0269 Effective date: 19860411 |
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AS | Assignment |
Owner name: CONNECTICUT BANK AND TRUST COMPANY, THE,,CONNECTIC Free format text: SECURITY INTEREST;ASSIGNOR:REHEIS, INC.;REEL/FRAME:004780/0781 Effective date: 19871001 Owner name: CONNECTICUT BANK AND TRUST COMPANY, THE, Free format text: SECURITY INTEREST;ASSIGNOR:REHEIS, INC.;REEL/FRAME:004780/0781 Effective date: 19871001 |
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AS | Assignment |
Owner name: REHEIS, INC. Free format text: CHANGE OF NAME;ASSIGNOR:REHEIS CHEMICAL COMPANY, INC.;REEL/FRAME:005001/0518 Effective date: 19870911 |